Metastasis of lung carcinoma to breast and vice versa accounts for one of the vast majority of cancer deaths. Synergistic treatments are proven to be the effective method to inhibit malignant cell proliferation. It is highly advantageous to use the minimum amount of a potent toxic drug, such as paclitaxel (Ptx) in ng/ml together with a natural and safe anticancer drug, curcumin (Cur) to reduce the systemic toxicity. However, both Cur and Ptx suffer from poor bioavailability. Herein, a drug delivery cargo was engineered by functionalizing reduced graphene oxide (G) with an amphiphilic polymer, PF-127 (P) by hydrophobic assembly. The drugs were loaded via pi-pi interactions, resulting in a nano-sized GP-Cur-Ptx of 140 nm. A remarkably high Cur loading of 678 wt.% was achieved, the highest thus far compared to any other Cur nanoformulations. Based on cell proliferation assay, GP-Cur-Ptx is a synergistic treatment (CI
This study reports on a facile and economical method for the scalable synthesis of few-layered graphene sheets by the microwave-assisted functionalization. Herein, single-layered and few-layered graphene sheets were produced by dispersion and exfoliation of functionalized graphite in ethylene glycol. Thermal treatment was used to prepare pure graphene without functional groups, and the pure graphene was labeled as thermally-treated graphene (T-GR). The morphological and statistical studies about the distribution of the number of layers showed that more than 90% of the flakes of T-GR had less than two layers and about 84% of T-GR were single-layered. The microwave-assisted exfoliation approach presents us with a possibility for a mass production of graphene at low cost and great potentials in energy storage applications of graphene-based materials. Owing to unique surface chemistry, the T-GR demonstrates an excellent energy storage performance, and the electrochemical capacitance is much higher than that of the other carbon-based nanostructures. The nanoscopic porous morphology of the T-GR-based electrodes made a significant contribution in increasing the BET surface as well as the specific capacitance of graphene. T-GR, with a capacitance of 354.1 Fg(-1) at 5 mVs(-1) and 264 Fg(-1) at 100 mVs(-1), exhibits excellent performance as a supercapacitor.
Measurement of the uric acid level in the body can be improved by biosensing with respect to the accuracy, sensitivity and time consumption. This study has reported the immobilization of uricase onto graphene oxide (GO) and its function for electrochemical detection of uric acid. Through chemical modification of GO using 1-ethyl-3-(dimethylaminopropyl) carbodiimide (EDC) and N-hydroxysulfosuccinimide (NHS) as cross-linking reagents, the enzyme activity of the immobilized uricase was much comparable to the free enzyme with 88% of the activity retained. The modified GO-uricase (GOU) was then subjected to electrocatalytic detection of uric acid (UA) via cyclic voltammetry (CV). For that reason, a glassy carbon electrode (GCE) was modified by adhering the GO along with the immobilized uricase to facilitate the redox reaction between the enzyme and the substrate. The modified GOU/GCE outperformed a bare electrode through the electrocatalytic activity with an amplified electrical signal for the detection of UA. The electrocatalytic response showed a linear dependence on the UA concentration ranging from 0.02 to 0.49 mM with a detection limit of 3.45 μM at 3σ/m. The resulting biosensor also exhibited a high selectivity towards UA in the presence of other interference as well as good reproducibility.
The deposition of a thin graphene film atop a chip scale piezoelectric substrate on which surface acoustic waves are excited is observed to enhance its performance for fluid transport and manipulation considerably, which can be exploited to achieve further efficiency gains in these devices. Such gains can then enable complete integration and miniaturization for true portability for a variety of microfluidic applications across drug delivery, biosensing and point-of-care diagnostics, among others, where field-use, point-of-collection or point-of-care functionality is desired. In addition to a first demonstration of vibration-induced molecular transport in graphene films, we show that the coupling of the surface acoustic wave gives rise to antisymmetric Lamb waves in the film which enhance molecular diffusion and hence the flow through the interstitial layers that make up the film. Above a critical input power, the strong substrate vibration displacement can also force the molecules out of the graphene film to form a thin fluid layer, which subsequently destabilizes and breaks up to form a mist of micron dimension aerosol droplets. We provide physical insight into this coupling through a simple numerical model, verified through experiments, and show several-fold improvement in the rate of fluid transport through the film, and up to 55% enhancement in the rate of fluid atomization from the film using this simple method.
In the present work, the microstructure, corrosion, and bioactivity of graphene oxide (GO) coating on the laser-modified and -unmodified surfaces of TiNb shape memory alloys (SMAs) were investigated. The surface morphology and chemical composition was examined using field emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD). The surface modification was carried out via a femtosecond laser with the aim to increase the surface roughness, and thus increase the adhesion property. FE-SEM analysis of the laser-treated Ti-30at.% Nb revealed the increase in surface roughness and oxygen/nitrogen containing groups on the Ti-30at.% Nb surface after being surface modified via a femtosecond laser. Furthermore, the thickness of GO was increased from 35μm to 45μm after the surface was modified. Potentiodynamic polarisation and electrochemical impedance spectroscopy studies revealed that both the GO and laser/GO-coated samples exhibited higher corrosion resistance than that of the uncoated TiNb SMA sample. However, the laser/GO-coated sample presented the highest corrosion resistance in SBF at 37°C. In addition, during soaking in the simulated body fluid (SBF), both the GO and laser/GO coating improved the formation of apatite layer. Based on the bioactivity results, the GO coating exhibited a remarkable antibacterial activity against gram-negative bacteria compared with the uncoated. In conclusion, the present results indicate that Ti-30at.% Nb SMAs may be promising alternatives to NiTi for certain biomedical applications.
This paper presents the fabrication of a highly sensitive and selective glucose sensor based on cuprous oxide/graphene nanocomposites-modified glassy carbon electrode (Cu2O/graphene/GCE). The Cu2O/graphene nanocomposites were synthesized based on a simple and straightforward chemical reduction process in alkaline aqueous solution using sodium carbonate as reductant. The size and shape of Cu2O nanoparticles on graphene sheets can be controlled by changing the amount of graphene oxide added during reaction. The electrochemical properties of Cu2O/graphene/GCE in 0.1M phosphate buffer solution were investigated by cyclic voltammetry and electrochemical impedance spectroscopy. It was found that the pH, concentration of supporting electrolyte, and scan rate had very crucial effect on the sensitivity of prepared sensor towards glucose oxidation. At an applied potential of +0.50V, the Cu2O/graphene/GCE presented a high sensitivity of 1330.05μAmM(-1)cm(-2) and fast response (within 3s). The amperometric non-enzymatic glucose sensor developed had a linear relationship from 0.01mM to 3.0mM glucose and detection limit of 0.36μM. In the presence of ascorbic acid, uric acid, dopamine, chloride and citrate ion and other carbohydrates, the interferences were negligible. The proposed sensor was successfully applied for the determination of glucose concentration in real human blood samples.
This paper focuses on the synthesis and mechanism of carbon nanospheres (CNS) coated with few- and multi-layered graphene (FLG, MLG). The graphitic carbon encapsulates the core/shell structure of the Ni/NiO nanoparticles via the chemical vapor deposition (CVD) method. The application of the resulting CNS and hybrids of CNS-FLG and CNS-MLG as reinforcement nanofillers in a polypropylene (PP) matrix were studied from the aspects of mechanical and thermal characteristics. In this research, to synthesize carbon nanostructures, nickel nitrate hexahydrate (Ni(NO₃)₂·6H₂O) and acetylene (C₂H₂) were used as the catalyst source and carbon source, respectively. Besides, the morphology, structure and graphitization of the resulting carbon nanostructures were investigated. On the other hand, the mechanisms of CNS growth and the synthesis of graphene sheets on the CNS surface were studied. Finally, the mechanical and thermal properties of the CNS/PP, CNS-FLG/PP, and CNS-MLG/PP composites were analyzed by applying tensile test and thermogravimetric analysis (TGA), respectively.
Fouling of marine surfaces has been a perpetual problem ever since the days of the early sailors. The tenacious attachment of seaweed and invertebrates to man-made surfaces, notably on ship hulls, has incurred undesirable economic losses. Graphene receives great attention in the materials world for its unique combination of physical and chemical properties. Herein, we present a novel 2-step synthesis method of graphene-silver nanocomposites which bypasses the formation of graphene oxide (GO), and produces silver nanoparticles supported on graphene sheets through a mild hydrothermal reduction process. The graphene-Ag (GAg) nanocomposite combines the antimicrobial property of silver nanoparticles and the unique structure of graphene as a support material, with potent marine antifouling properties. The GAg nanocomposite was composed of micron-scaled graphene flakes with clusters of silver nanoparticles. The silver nanoparticles were estimated to be between 72 and 86nm (SEM observations) while the crystallite size of the silver nanoparticles (AgNPs) was estimated between 1 and 5nm. The nanocomposite also exhibited the SERS effect. GAg was able to inhibit Halomonas pacifica, a model biofilm-causing microbe, from forming biofilms with as little as 1.3wt.% loading of Ag. All GAg samples displayed significant biofilm inhibition property, with the sample recording the highest Ag loading (4.9wt.% Ag) associated with a biofilm inhibition of 99.6%. Moreover, GAg displayed antiproliferative effects on marine microalgae, Dunaliella tertiolecta and Isochrysis sp. and inhibited the growth of the organisms by more than 80% after 96h. The marine antifouling properties of GAg were a synergy of the biocidal AgNPs anchored on the stable yet flexible graphene sheets, providing maximum active contact surface areas to the target organisms.
In this paper, we report how few layers graphene that can be produced in large quantity with low defect ratio from exfoliation of graphite by using a high intensity probe sonication in water containing liquid hand soap and PVP. It was founded that the graphene powder obtained by this simple exfoliation method after the heat treatment had an excellent exfoliation into a single or layered graphene sheets. The UV-visible spectroscopy, FESEM, TEM, X-ray powder diffraction and Raman spectroscopy was used to analyse the graphene product. The thermal diffusivity of the samples was analysed using a highly accurate thermal-wave cavity photothermal technique. The data obtained showed excellent enhancement in the thermal diffusivity of the graphene dispersion. This well-dispersed graphene was then used to fabricate an electrically conductive polymer-graphene film composite. The results demonstrated that this low cost and environmental friendly technique allowed to the production of high quality layered graphene sheets, improved the thermal and electrical properties. This may find use in the wide range of applications based on graphene.
A photoelectrochemical (PEC) sensor with excellent sensitivity and detection toward copper (II) ions (Cu2+) was developed using a cadmium sulphide-reduced graphene oxide (CdS-rGO) nanocomposite on an indium tin oxide (ITO) surface, with triethanolamine (TEA) used as the sacrificial electron donor. The CdS nanoparticles were initially synthesized via the aerosol-assisted chemical vapor deposition (AACVD) method using cadmium acetate and thiourea as the precursors to Cd2+ and S2-, respectively. Graphene oxide (GO) was then dip-coated onto the CdS electrode and sintered under an argon gas flow (50 mL/min) for the reduction process. The nanostructured CdS was adhered securely to the ITO by a continuous network of rGO that also acted as an avenue to intensify the transfer of electrons from the conduction band of CdS. The photoelectrochemical results indicated that the ITO/CdS-rGO photoelectrode could facilitate broad UV-visible light absorption, which would lead to a higher and steady-state photocurrent response in the presence of TEA in 0.1 M KCl. The photocurrent decreased with an increase in the concentration of Cu2+ ions. The photoelectrode response for Cu2+ ion detection had a linear range of 0.5-120 μM, with a limit of detection (LoD) of 16 nM. The proposed PEC sensor displayed ultra-sensitivity and good selectivity toward Cu2+ ion detection.
Zinc selenide/graphene oxide (ZnSe/GO) composite is synthesized using hydrothermal method. Two different methods
such as direct and indirect route have been investigated to form the ZnSe/GO composite. In this research, the graphene
oxide used was in sheet and liquid form. The synthesized composite was then characterized using X-ray diffraction (XRD)
for phase identification, field emission scanning electron microscopy (FESEM) for morphology analysis and ultravioletvisible
spectroscopy (UV-Vis) for optical properties. ZnSe/GO composite showed absorption peak ranging from 460 to
480 nm with the optical band gap obtained through Tauc equation. The optical band gap of the ZnSe/GO composite has
been tuned down to a smaller value as compared to the bulk ZnSe compound. The optical band gap has been reduced
to around 2.53 eV when liquid graphene oxide was used while around 2.23 to 2.32 eV when graphene oxide sheet was
used. The purity of ZnSe/GO composite synthesis via indirect hydrothermal method is higher than those synthesized via
direct hydrothermal method. The type of graphene oxide will affect the morphology of the composite where the ZnSe
compound was either wrapped by tiny thorn-like substance or graphene oxide layer.
Incorporation of silver nanomaterial into polymer matrix can further accomplished their potential usage in real life
applications. In our previous study, silver nanoparticles (AgNPs) and silver-graphene oxide nanocomposites (AgGO)
were prepared via a rapid microwave-assisted method. Hereby, the as-synthesized AgNPs or AgGO was dispersed in a
chitosan solution. Subsequently, the resultant mixture solution was further coagulated in a coagulation bath containing
sodium hydroxide via a neutralization process. This resulted in the formation of spherical-shaped chitosan beads.
The structure of the beads showed that the chitosan beads embedded with AgGO exhibited a more porous structure as
compared to the plain chitosan beads. Furthermore, the chitosan beads containing AgNPs or AgGO were tested for
their antibacterial activity against Escherichia coli and Staphylococcus aureus. The antibacterial results indicated that
the silver nanomaterial contained chitosan beads could effectively inhibit the growth of both E. coli and S. aureus as
compared to the bare chitosan beads. The produced chitosan nanocomposite envisioned that can be potentially employed
for water disinfection purpose.
Generally, in a waveguide-based humidity sensors, increasing the relative humidity (RH) causes the cladding refractive index (RI) to increase due to cladding water absorption. However, if graphene oxide (GO) is used, a reverse phenomenon is seen due to a gap increase in graphene layers. In this paper, this interesting property is applied in order to fabricate differential humidity sensor using the difference between RI of reduced GO (rGO) and nano-anatase TiO2 in a chip. First, a new approach is proposed to prepare high quality nano-anatase TiO2 in solution form making the fabrication process simple and straightforward. Then, the resulted solutions (TiO2 and GO) are effortlessly drop casted and reduced on SU8 two channels waveguide and extensively examined against several humid conditions. Investigating the sensitivity and performance (response time) of the device, reveals a great linearity in a wide range of RH (35% to 98%) and a variation of more than 30 dB in transmitted optical power with a response time of only ~0.7 sec. The effect of coating concentration and UV treatment are studied on the performance and repeatability of the sensor and the attributed mechanisms explained. In addition, we report that using the current approach, devices with high sensitivity and very low response time of only 0.3 sec can be fabricated. Also, the proposed device was comprehensively compared with other state of the art proposed sensors in the literature and the results were promising. Since high sensitivity ~0.47dB/%RH and high dynamic performances were demonstrated, this sensor is a proper choice for biomedical applications.
A new graphene-based tetraethoxysilane-methyltrimethoxysilane sol-gel hybrid magnetic nanocomposite (Fe3O4@G-TEOS-MTMOS) was synthesised, characterized and successfully applied in magnetic solid-phase extraction (MSPE) for simultaneous analysis of polar and non-polar organophosphorus pesticides from several water samples. The Fe3O4@G-TEOS-MTMOS nanocomposite was characterized using Fourier transform-infrared spectroscopy, energy-dispersive X-ray spectroscopy, field emission scanning electron microscopy and X-ray diffraction. Separation, determination and quantification were achieved using gas chromatography coupled with micro electron capture detector. Adsorption capacity of the sorbent was calculated using Langmuir equation. MSPE was linear in the range 100-1000 pg mL(-1) for phosphamidon and dimethoate, and 10-100 pg mL(-1) for chlorpyrifos and diazinon, with limit of detection (S/N = 3) of 19.8, 23.7, 1.4 and 2.9 pg mL(-1) for phosphamidon, dimethoate, diazinon and chlorpyrifos, respectively. The LODs obtained is well below the maximum residual level (100 pg mL(-1)) as set by European Union for pesticides in drinking water. Acceptable precision (%RSD) was achieved for intra-day (1.3-8.7%, n = 3) and inter-day (7.6-17.8%, n = 15) analyses. Fe3O4@G-TEOS-MTMOS showed high adsorption capacity (54.4-76.3 mg g(-1)) for the selected OPPs. No pesticide residues were detected in the water samples analysed. Excellent extraction recoveries (83-105%) were obtained for the spiked OPPs from tap, river, lake and sea water samples. The newly synthesised Fe3O4@G-TEOS-MTMOS showed high potential as adsorbent for OPPs analysis.
This work demonstrates the high performance graphene oxide (GO)/PEDOT:PSS doubled decked hole transport layer (HTL) in the PCDTBT:PC71BM based bulk heterojunction organic photovoltaic device. The devices were tested on merits of their power conversion efficiency (PCE), reproducibility, stability and further compared with the devices with individual GO or PEDOT:PSS HTLs. Solar cells employing GO/PEDOT:PSS HTL yielded a PCE of 4.28% as compared to either of individual GO or PEDOT:PSS HTLs where they demonstrated PCEs of 2.77 and 3.57%, respectively. In case of single GO HTL, an inhomogeneous coating of ITO caused the poor performance whereas PEDOT:PSS is known to be hygroscopic and acidic which upon direct contact with ITO reduced the device performance. The improvement in the photovoltaic performance is mainly ascribed to the increased charge carriers mobility, short circuit current, open circuit voltage, fill factor, and decreased series resistance. The well matched work function of GO and PEDOT:PSS is likely to facilitate the charge transportation and an overall reduction in the series resistance. Moreover, GO could effectively block the electrons due to its large band-gap of ~3.6 eV, leading to an increased shunt resistance. In addition, we also observed the improvement in the reproducibility and stability.
In this study, a sonochemical approach was utilised for the development of graphene-gold (G-Au) nanocomposite. Through the sonochemical method, simultaneous exfoliation of graphite and the reduction of gold chloride occurs to produce highly crystalline G-Au nanocomposite. The in situ growth of gold nanoparticles (AuNPs) took place on the surface of exfoliated few-layer graphene sheets. The G-Au nanocomposite was characterised by UV-vis, XRD, FTIR, TEM, XPS and Raman spectroscopy techniques. This G-Au nanocomposite was used to modify glassy carbon electrode (GCE) to fabricate an electrochemical sensor for the selective detection of nitric oxide (NO), a critical cancer biomarker. G-Au modified GCE exhibited an enhanced electrocatalytic response towards the oxidation of NO as compared to other control electrodes. The electrochemical detection of NO was investigated by linear sweep voltammetry analysis, utilising the G-Au modified GCE in a linear range of 10-5000μM which exhibited a limit of detection of 0.04μM (S/N=3). Furthermore, this enzyme-free G-Au/GCE exhibited an excellent selectivity towards NO in the presence of interferences. The synergistic effect of graphene and AuNPs, which facilitated exceptional electron-transfer processes between the electrolyte and the GCE thereby improving the sensing performance of the fabricated G-Au modified electrode with stable and reproducible responses. This G-Au nanocomposite introduces a new electrode material in the sensitive and selective detection of NO, a prominent biomarker of cancer.
The transformation of systematic vacuum and hydrogen annealing effects in graphene devices on the SiO2 surface is reported based on experimental and van der Waals interaction corrected density functional theory (DFT) simulation results. Vacuum annealing removes p-type dopants and reduces charged impurity scattering in graphene. Moreover, it induces n-type doping into graphene, leading to the improvement of the electron mobility and conductivity in the electron transport regime, which are reversed by exposing to atmospheric environment. On the other hand, annealing in hydrogen/argon gas results in smaller n-type doping along with a decrease in the overall conductivity and carrier mobility. This degradation of the conductivity is irreversible even the graphene devices are exposed to ambience. This was clarified by DFT simulations: initially, silicon dangling bonds were partially terminated by hydrogen, subsequently, the remaining dangling bonds became active and the distance between the graphene and SiO2 surface decreased. Moreover, both annealing methods affect the graphene channel including the vicinity of the metal contacts, which plays an important role in asymmetric carrier transport.
The chemical route of producing geranyl propionate involves the use of toxic chemicals, liberation of unwanted by-products as well as problematic separation process. In view of such problems, the use of Rhizomucor miehei lipase (RML) covalently bound onto activated chitosan-graphene oxide (RML-CS/GO) support is suggested. Following analyses using Fourier transform infrared spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, and thermogravimetry, properties of the RML-CS/GO were characterized. A response surface methodological approach using a 3-level-four-factor (incubation time, temperature, substrate molar ratio, and stirring rate) Box-Behnken design was used to optimize the experimental conditions to maximize the yield of geranyl propionate. Results revealed that 76 ± 0.02% of recovered protein had yielded 7.2 ± 0.04 mg g(-1) and 211 ± 0.3% U g(-1) of the maximum protein loading and esterification activity, respectively. The actual yield of geranyl propionate (49.46%) closely agreed with the predicted value (49.97%) under optimum reaction conditions (temperature: 37.67°C, incubation time: 10.20 hr, molar ratio (propionic acid:geraniol): 1:3.28, and stirring rate: 100.70 rpm) and hence, verifying the suitability of this approach. Since the method is performed under mild conditions, the RML-CS/GO biocatalyst may prove to be an environmentally benign alternative for producing satisfactory yield of geranyl propionate.
Low-temperature growth, as well as the transfer free growth on substrates, is the major concern of graphene research for its practical applications. Here we propose a simple method to achieve the transfer free graphene growth on SiO2 covered Si (SiO2/Si) substrate at 250 °C based on a solid-liquid-solid reaction. The key to this approach is the catalyst metal, which is not popular for graphene growth by chemical vapor deposition. A catalyst metal film of 500 nm thick was deposited onto an amorphous C (50 nm thick) coated SiO2/Si substrate. The sample was then annealed at 250 °C under vacuum condition. Raman spectra measured after the removal of the catalyst by chemical etching showed intense G and 2D peaks together with a small D and intense SiO2 related peaks, confirming the transfer free growth of multilayer graphene on SiO2/Si. The domain size of the graphene confirmed by optical microscope and atomic force microscope was about 5 μm in an average. Thus, this approach will open up a new route for transfer free graphene growth at low temperatures.